Catalytic hydrotreatment of pyrolytic lignins from different sources to biobased chemicals:Identification of feed-product relations

The pyrolysis liquid biorefinery concept involves separation of pyrolysis liquids in various fractions followed by conversion of the fractions to value-added products. Pyrolytic lignins (PLs), the water-insoluble fractions of pyrolysis liquids, are heterogeneous, cross linked oligomers composed of substituted phenolics whose structure and physicochemical properties vary significantly depending on the biomass source. The catalytic hydrotreatment of six PLs from different biomass sources (pine, prunings, verge grass, miscanthus and sunflower seed peel) was investigated to determine the effect of different feedstocks on the final product composition and particularly the amount of alkylphenolics and aromatics, the latter being important building blocks for the chemical industry. Hydrotreatment was performed with Pd/C, 100 bar of hydrogen pressure and temperatures in the range of 350–435 °C, resulting in depolymerized product mixtures with monomer yields up to 39.1 wt% (based on PL intake). The molecular composition of the hydrotreated oils was shown to be a strong function of the PL feed and reaction conditions. Statistical analyses provided the identification of specific structural drivers on the formation of aromatics and phenolics, and a simple model able to accurately predict the yields of such monomers after catalytic hydrotreatment was obtained (R2 = 0.9944) and cross-validated (R2 = 0.9326). These feed-product relations will support future selections of PL feeds to obtain the highest amounts of valuable biobased chemicals

Pyrolytic lignin:A promising biorefinery feedstock for the production of fuels and valuable chemicals

Lignocellulosic biomass is a key feedstock for the sustainable production of biofuels, biobased chemicals and performance materials. Biomass can be efficiently converted into pyrolysis liquids (also known as bio-oils) by the well-established fast pyrolysis technology. Currently, there is significant interest in the application of fast pyrolysis technology as principle biomass conversion technology due to its feedstock flexibility, low cost and high energy conversion efficiency, with many emerging commercial enterprises being established around the globe. Upgrading of the bio-oils is a requisite, and is complicated by its complex and heterogeneous organic nature. Pyrolysis liquids may be further separated by a simple water fractionation, yielding an aqueous sugar-rich phase and a water-insoluble pyrolytic lignin (PL) fraction. This separation step allows the use of dedicated conversion strategies for each fraction, which can be highly advantageous due to their differences in composition and reactivity. For example, the sugar-rich fractions can be used for fermentation, while the phenolic-rich PL is a particularly promising feedstock for the production of a wide range of platform chemicals and energy-dense streams upon depolymerization. To aid the emerging use of PL, novel characterization techniques and valorization strategies are being explored. In this review, the fast pyrolysis process and PL characterization efforts are discussed in detail, followed by the state-of-the-art regarding PL processing using both oxidative and reductive (catalytic) strategies, as well as a combination thereof. Possible applications are discussed and recommendations for future research are provided

Ni-Based Catalysts for the Hydrotreatment of Fast Pyrolysis Oil

Catalytic hydrotreatment is an attractive technology to convert fast pyrolysis oil to stabilized oil products for co processing in conventional crude oil refinery units. We report here the use of novel bimetallic NiCu- and NiPd-based (Picula) catalysts characterized by a high Ni content (29-58 wt %) and prepared using a sol gel method with SiO2, La2O3, kaolin, ZrO2, and combinations thereof as the support, for the catalytic hydrotreatment of fast pyrolysis oil. The experiments were performed in a batch autoclave (1 h at 150 degrees C, 3 h at 350 degrees C, and 200 bar initial pressure at 350 degrees C). The catalyst with the highest nickel loading (58 wt % Ni) promoted with Pd (0.7 wt %) was the most active, yielding oil products with improved properties compared to the crude pyrolysis oil (lower oxygen content, higher solubility in hydrocarbons, and less tendency for coke formation). For all Picula catalysts, except the ZrO2-based catalysts, methane formation was considerably lower than for Ru/C, the benchmark catalyst in catalytic hydrotreatment of fast pyrolysis oil. To anticipate possible catalyst deactivation at very long times on stream, catalyst regeneration studies were performed using thermogravimetric analysis. Analyses of the regenerated catalysts (X-ray diffraction, high-resolution transmission electron microscopy, and Brunauer Emmett Teller surface area) showed the occurrence of active metal agglomeration.</p

Quantum simulation of thermodynamics in an integrated quantum photonic processor

One of the core questions of quantum physics is how to reconcile the unitary evolution of quantum states, which is information-preserving and time-reversible, with evolution following the second law of thermodynamics, which, in general, is neither. The resolution to this paradox is to recognize that global unitary evolution of a multi-partite quantum state causes the state of local subsystems to evolve towards maximum-entropy states. In this work, we experimentally demonstrate this effect in linear quantum optics by simultaneously showing the convergence of local quantum states to a generalized Gibbs ensemble constituting a maximum-entropy state under precisely controlled conditions, while introducing an efficient certification method to demonstrate that the state retains global purity. Our quantum states are manipulated by a programmable integrated quantum photonic processor, which simulates arbitrary non-interacting Hamiltonians, demonstrating the universality of this phenomenon. Our results show the potential of photonic devices for quantum simulations involving non-Gaussian states

Sex differences in the timing of identification among children and adults with autism spectrum disorders

To examine differences by sex in the timing of identification of individuals with autism spectrum disorders (ASD), survey data were collected in the Netherlands from 2,275 males and females with autistic disorder, Asperger's syndrome and PDD-NOS. Among participants <18 years of age, females with Asperger's syndrome were identified later than males. Among participants ≥18 years of age, females with autistic disorder were identified later than males. In more recent years, girls with Asperger's syndrome are diagnosed later than boys, confirming earlier findings. In adults, the delayed timing of diagnosis in females with autistic disorder may be related to changing practices in diagnosis over time. Strategies for changing clinician behaviour to improve recognition of ASD in females are needed. © 2012 Springer Science+Business Media, LLC

Reaction Chemistry and Kinetics of Corn Stalk Pyrolysis without and with Ga/HZSM-5

The bifunctional Ga/HZSM-5 catalyst has been proven having the capability to increase the selectivity of aromatics production during catalytic pyrolysis of furan and woody biomass. However, the reaction chemistry and kinetics of pyrolysis of herbaceous biomass promoted by Ga/HZSM-5 is rarely reported. Pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) analysis and non-isothermal thermogravimetric analysis at four heating rates were carried out to investigate the decomposition behavior and pyrolysis kinetics of corn stalk without and with Ga/HZSM-5. The effective activation energies for corn stalk pyrolysis were calculated by using the Friedman isoconversional method. The Py–GC/MS analysis results indicated that the Ga/HZSM-5 catalyst had a high selectivity toward producing the aromatic chemicals of xylene, toluene and benzene, whereas the major products from non-catalytic pyrolysis of corn stalk were oxygenated compounds. The presence of Ga/HZSM-5 could significantly reduce the effective activation energies of corn stalk pyrolysis from 159.9–352.4 kJ mol−1 to 41.6–99.8 kJ mol−1 in the conversion range of 0.10–0.85

Mono-, bi-, and tri-metallic Ni-based catalysts for the catalytic hydrotreatment of pyrolysis liquids

Catalytic hydrotreatment is a promising technology to convert pyrolysis liquids into intermediates with improved properties. Here, we report a catalyst screening study on the catalytic hydrotreatment of pyrolysis liquids using bi- and tri-metallic nickel-based catalysts in a batch autoclave (initial hydrogen pressure of 140 bar, 350 A degrees C, 4 h). The catalysts are characterized by a high nickel metal loading (41 to 57 wt%), promoted by Cu, Pd, Mo, and/or combination thereof, in a SiO2, SiO2-ZrO2, or SiO2-Al2O3 matrix. The hydrotreatment results were compared with a benchmark Ru/C catalyst. The results revealed that the monometallic Ni catalyst is the least active and that particularly the use of Mo as the promoter is favored when considering activity and product properties. For Mo promotion, a product oil with improved properties viz. the highest H/C molar ratio and the lowest coking tendency was obtained. A drawback when using Mo as the promoter is the relatively high methane yield, which is close to that for Ru/C. H-1, C-13-NMR, heteronuclear single quantum coherence (HSQC), and two-dimensional gas chromatography (GC x GC) of the product oils reveal that representative component classes of the sugar fraction of pyrolysis liquids like carbonyl compounds (aldehydes and ketones and carbohydrates) are converted to a large extent. The pyrolytic lignin fraction is less reactive, though some degree of hydrocracking is observed